Diazo-preparations and process of making same



Patented Feb. 23, 1932 UNITED STATES A- NT FFICE HANS JOHNER, or BASEL, sw rrznnminn; assrenon. 3mm, or chairman mnus'rny in menu, or BASELLSWITZERLAND 1 1 nrazo-ranrmmronsann rnocnss or MAKING same 11.. Drawing. Application filed June 10, msaserial 11No. 460,29 and 11'. Switzerland June 17, 1929.

It is known that diam-preparations can be made by precipitating a diazo-solution with an aromatic sulfonic acid. 1 .1 y

This procedure is not of ,generalapplicao cation, since many diazo-compoundsare not precipitated or only incompletely precipitated by an aromatic sulfonic acid.

This invention achieves in many cases an essential improvement in the separation of 15 the diam-compound, by conducting the precipitation by means of such aromatic sulfonic acids of the benzene or ofthe naphthalene series which contain more than one sulfogroup in presence of a salt of a metal of the second series of the periodic system ofthe 1 elements, advantageously a salt of 1 magnesium. 1 1

i The products thus precipitated contain a metal, probablyin the form ofadouble compound, and are characterized by their good solubility, which is remarkable in view of the ease with which they are precipitated. They are very stable and well suited for the production of dyeings by the methods hitherto usual in the so-called ice dyeing or printing. The new products correspond very probably with the general formula As to the aromatic polyvalent sulfonic acids of the benzene or of the naphthalene 1 series which are available, there may be named inter alia the benzene-sulfonic acids, toluene-sulfonic acids, chlorobenzene-sulfonic acids, chlorotoluene-sulfonie acids, naphthalene-sulfonic acids, chloro-naphthaleneand the clear diazo-solution ismixed while sulfonicacids which contain more than one sulfo-group. 1 1 1 The following examples illustrate the invent1on, the parts being by weight 1- Example 1 220 parts of 2: 5 dichloraniline-hydrochloride areintroduced into 400 parts of ice and QQO partsbyvolurne of hydrochloric acid, and diazotized byfaddition of the necessary proportion of nitritisolution. Into the diaz osolutionareintroduced 200 parts of pulverized magnesium chloride (MgGhLGH O).

ll'literthesalt is dissolved the whole is filtered stirring with 300 partsof'sodium m-benzenedisul'lfonate. Thereis soon formed a white crystalline precipitate. This is filtered, pressed and dried in a vacuum atBO-lO G. \Vhen the operation is conductedwithout the use of magnesium chloride no diazo-compound is precipitated, even by addition of common salt. 1 1

' The new diazo-compound is very freely soluble in Water and corresponds very probably with the formula 1 Also with l-ltoluenedisulfonic acid or 1 :2: a -chlorobenzenedisulfonic acid or, re spectively, naphthalene-2 7 -dis1ilfonic acid or, naphthalenefl: 3: 6-trisulfonic acid, there are obtainedvaluable d-oublesalts. An analogous calcium double salt is also obtained with aid. of naphthalene-2 7- disulfonic acid and calcium chloride. e e y Example 2 I 25 parts ofortho-anisi'dine are mixed with 48 parts by volume of concentrated hydrochloric acid and the mixture is cooled externallyiby means or ice, while it is strongly stirred. To the suspension of the hydrochloride thus obtained, with addition of only a little ice or without such additiomthere are gradually added 4 0;parts by volume of a .5151- sodium-nitritesolution. When the diazotiza-v 100 fonic acids, chlorobenzenedlsulfomc acids; from tion is complete 21 parts of crystallized magnesium chloride are added and the solution is then filtered. To the clear diazo-solution V "ter, from which it maybe recrystallized. It

corresponds very probably with the formula 00H; com

Example 3 i I 52 parts of ortho-chloraniline are stirred with 100 parts of water and IOU parts by volume of concentratedhydrochloric acid,

the suspension is cooled-in ice and 80 volumes of '5N sodium-nitrite solution are gradually dropped in. When diazotization complete 82 parts ofpowdered crystallized magnesium chloride are added, and the solution is then filtered. A boiling hot concentrated solution of 90 parts ofsodium 1 :"5-naphthalene disulfonate is nowaddedto the clear diazo-solut'on. n oolin .there cr stallizes a mail T J i 1 O c y thereof by means of SLlCl'lrflJOlDfllllC;Sl'llfOlllC White precipitate, which is .filtered, freed from liquid by suction or pressure and dried in a vacuum'at -40 C The product is very stable and freely soluble in- Water, from which it can be recrystallized. It corresponds very probably with the formula V SOs-ME-SO:

III N Further valuableprecipitates are also obtained from .diazotized i ortho nitraniline, magnesium chloride and 1 :2 4-toluenedisulacid, chloronaphthalenedisulfonic 'diazotized metanitraniline, magnesium chlo- V diazotized para=nitraniline, magnesium 'chlo- *rid and 1:2:4echolorbenzenedisulfonlc ride and 1: 2 t-toluenedisulfonioacid from acid or naphthalene- 1: 3 6-trisulfonic acid; from diazotized -1-chloro Q amin-odiphenylether, magnesium chloride and 1:2:4-toluenedisulfonic acid; from diazotized 4-nitroortho-toluidine, magnesium chloride and 'chloronaphthalenedisulfonic acid; from. diazotized 3-nitro-para-toluidine, magnesium chloride and l:2:4 chlorobenzenedisulfonic acid {fromdiazotized aminoazobenzene, mag

nesium chloride and benzene-1:3 disulfonic manna so forth, it'being a matter of course that Othersuitable magnesium salts, suchas *mag'nesiiun sulfate, magnesium bromide, -or

magnesiumsalts. V v l3; Apr-ocess for themanufacture OfISQlid,

thelike, may be substituted for the magnesium chloride. 7 r

If necessary the solubility of the new diazo-compounds can be increased by addition of acid or an easily soluble'neutral or acid salt (compare U. S. Patent 1,629,906).

What I claim is 1. A process for the manufacture of solid,

stable" diazo-preparations, consisting in precipitating diam-compounds ofthe benzene series: from solutions thereof by means of such aromatic sulfonic acids of the benzene and of the naphthaleneseries which contain more than one sulfo-group in presence of salts of, such metals of the second group of the periodic system of -the elements the hydroXides of Whichare strong-bases.

2.' A process for the manufacture of solid, stable .diazo-preparations, consisting in precipitating .diazo-compounds of the benzene series from 'SOlllUOIlS thereof by means of such aromatic 'sulfonic' acids of .the. benzene and of the naphthaleneseries which contain more than. one sulfo+group n presence of stable diazoapreparations, consistingin precipitating diazo-compounds deriving :from

mononuclear aromatic bases from solutions acids of the benzeneandxof the naphthalene seriesrwhich contain more than one sulfogroupin presence of magnesium salts.

4. A process for the manufacture of solid,

gstable diam-preparations, consisting in ,pre-- --c1,p1tating diazo-compounds deriving-from mononuclear aromatic bases of the benzene more than=- 0ne sulfo-group in presence of magnesium salts. A I

.5. A'process forzthe manufacture of solid,

series 'fromsolutions thereof by ;.means of 1 such lfiIOIHfltlC sulfonic ac ds of F the benzene and of the naphthalene series which contain 05 series from. solutions thereof by means of such aromatic sulfonic acids. of the benzene series which contain more than one sulfogroup-in presence of magnesium salts;

'6. A process for tliemanufactureof-solid,

stable diam-preparations, consisting. in precipitating diazo-compounds deriving :from

mononuclear aromatic bases :of the benzene series containing-halogen from solutions thereof by means of such:.aromat1c vsulfonic acids of the benzene #series which contain more'than one sulfo-group 1n rpresenceof 8. As new products the solid, stable diazocompounds of the general formula compounds of the general formula wherein R stands for the aryl radical of a diam-compound of the benzene series and R" for an aromatic nucleus of the benzene and of the naphthalene series, which products are soluble in water and couple with coupling components to form dyestuffs.

10. As new products the solid, stable diazocompounds of the general formula wherein R stands for the aryl radical of a mononuclear diazo-compound and R" for an aromatic nucleus of the benzene and of the naphthalene series, which products are soluble in water and couple with coupling compo nents to form dyestuffs.

11. As new products the solid, stable diazo-componds of the general formula wherein R stands for the aryl radical of a. halogenated diazo-compound of the benzene sereis and R for an aromatic nucleus of the benzene and of the naphthalene series, which products are soluble in water and couple with coupling components to form (1 estufis.

12. As new products the soli ,stable diazocompounds of the general formula wherein R" stands for an aromatic nucleus of the benzene series, which products are soluble in water and couple with coupling components to form dyestuffs.

13. As new products the solid, stable diazocompounds of the general formula wherein R stands for an aromatic nucleus of the benzene series in which the two SO,-

groups stand in meta-position toeach other, which products are soluble in water and cou ple with coupling components to form dyestufis.

14. As new products the solid, stable diazocompounds of the general formula wherein R stands for a toluene nucleus in which the two SO -groups stand in meta-position to each other,which products are soluble in water and couple with coupling components to form dyestuffs.

In witness whereof I have hereunto signed my name this 31st day of Ma 1930.

' HA S J OHNER. 

